WO1996038453A1 - Hydroxy functional alkoxysilane and alkoxysilane functional polyurethane made therefrom - Google Patents

Hydroxy functional alkoxysilane and alkoxysilane functional polyurethane made therefrom Download PDF

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Publication number
WO1996038453A1
WO1996038453A1 PCT/US1996/005433 US9605433W WO9638453A1 WO 1996038453 A1 WO1996038453 A1 WO 1996038453A1 US 9605433 W US9605433 W US 9605433W WO 9638453 A1 WO9638453 A1 WO 9638453A1
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group
groups
carbon atoms
alkoxysilane
branched
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PCT/US1996/005433
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English (en)
French (fr)
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Dean M. Moren
Ian R. Owen
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Minnesota Mining And Manufacturing Company
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Priority to DE69601634T priority Critical patent/DE69601634T2/de
Priority to JP53646196A priority patent/JP4016090B2/ja
Priority to EP96911810A priority patent/EP0833830B1/en
Publication of WO1996038453A1 publication Critical patent/WO1996038453A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00

Definitions

  • the present invention relates to hydroxy functional alkoxysilanes and moisture-curable alkoxysilane functional polyurethanes made therefrom.
  • the alkoxysilane functional polyurethanes may be used to provide moisture-curable adhesives, sealants, putties, coatings and the like.
  • Moisture-curable compositions cure in the presence of moisture to form crosslinked materials.
  • the moisture may be obtained from water vapor in the air or from the substrate to which the moisture- curable composition is applied.
  • Moisture-curable compositions may be used to provide adhesives, sealants, coatings and putties for numerous industries including aerospace and automotive industries. Moisture- curable compositions are advantageous because they do not require heat or solvents to cure.
  • Moisture-curable composition may comprise, for example, alkoxysilane or isocyanate functional polyurethanes, the alkoxysilane or isocyanate groups providing the active sites for the curing reaction with water.
  • Alkoxysilane functional polyurethanes are preferred over isocyanate functional polyurethanes because they are less toxic, and generally provide better storage and faster cure properties.
  • isocyanate functional polyurethanes may react with water to form carbon dioxide gas which can cause foaming and a decrease in the strength of the composition.
  • the resulting polyurethane is terminated at both ends with the moisture-reactive alkoxysilane groups to provide optimal curing and enhanced physical properties in the crosslinked material.
  • hydroxy functional alkoxysilane starting material can undergo an alcohol interchange reaction prior to reaction with the isocyanate functional polymer.
  • alcohol interchange see Metal Alkoxides. D. C. Bradley, R. C. Mehrotra, and D. P. Gaur, Academic Press, New York, 1978. See also Russian Journal Article (Zhurnal Obshchei Khimii Vol. 41, No. 4, page 933, April, 1977) which corroborates the alcohol interchange reaction for hydroxy functional alkoxysilanes having carbamate linkage.
  • the article describes the reaction of ethylene carbonate and aminosilanes to form hydroxyethyl(silylalkyl)carbamates, stating that when “...there are alkoxy substituents on the silicon atom, the main reaction is accompanied by processes of inter- and intra-molecular polycondensation with formation of oligomeric products.
  • the resulting polyurethane bears an inert terminus (COOR) that does not participate in the crosslinking reaction with moisture. As a consequence, the resulting polyurethane may not sufficiently cure, thus remaining too tacky and providing inadequate strength for some applications.
  • COOR inert terminus
  • the present invention provides a novel hydroxy functional alkoxysilane.
  • the hydroxy functional alkoxysilane is contaminated with less than 10 mole percent of a non-silane functional alcohol (ROH). More preferably, the hydroxy functional alkoxysilane is contaminated with less than 5 mole percent (most preferably less than 1 mole percent) of a non-silane functional alcohol.
  • the hydroxy functional alkoxysilane compound is a hydroxyalkylenecarbamoylalkylenealkoxysilane (hereinafter referred to as "hydroxycarbamoylsilane”) having the following structure:
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 9 is independently hydrogen; a linear, branched or cyclic alkyl group having 1 to 18 (preferably 1 to 6) carbon atoms, optionally comprising 1 to 3 non-terminal oxygen, sulfur, nitrogen or carbonyl groups in the hydrocarbon backbone of the alkyl group and optionally substituted with one or more hydroxy I groups; or an aryl group having 6 carbon atoms, optionally substituted with a haio, nitro or cyano group, or an alkyl, alkyloxy, alkylthio, dialkyiamino or carboalkyloxy group each having 1 to 18 (preferably 1 to 6) carbon atoms; with the proviso that at least one of R ⁇ , R 2 , R 3 , and R 4 is not hydrogen;
  • R ⁇ is hydrogen or a linear, branched or cyclic alkyl group having 1 to 18 (preferably 1 to 6) carbon atoms, optionally comprising 1 to 3 non-terminal oxygen, sulfur, nitrogen or carbonyl groups in the hydrocarbon backbone of the alkyl group;
  • R8 is a linear, branched or cyclic alkylene group having at least two (preferably 2 to 10) carbon atoms
  • R10 is a linear, branched, or cyclic alkyl group having at least 2 (preferably 2 to 6) carbon atoms, optionally comprising 1 to 3 non-terminal oxygen, sulfur, nitrogen or carbonyl groups in the hydrocarbon backbone of the alkyl group;
  • n 0, 1 or 2;
  • n 1, 2, or 3.
  • m is 0; one of the R 1 , R 2 , R 3 and R 4 groups is methyl with the remainder of these groups being hydrogen; R 7 is hydrogen; R 8 is
  • hydroxycarbamoylsilane may be formed by reaction of a substituted cyclic alkylene carbonate with an aminoalkylenealkoxysilane.
  • the cyclic alkylene carbonate has the following structure:
  • the aminoalkylenealkoxysilane has the following structure:
  • R 7 , R 8 , R 9 , R 10 and n are also as described above.
  • the present invention provides an alkoxysilane functional polyurethane having the structure:
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 8 and R 9 is independently hydrogen; a linear, branched or cyclic alkyl group having 1 to 18 (preferably 1 to 6) carbon atoms, optionally comprising 1 to 3 non-terminal oxygen, sulfur, nitrogen or carbonyl groups in the hydrocarbon backbone of the alkyl group and optionally substituted with one or more hydroxyl groups; or an aryl group having 6 carbon atoms, optionally substituted with a halo, nitro or cyano group, or an alkyl, alkyloxy, alkylthio, dialkylamino or carboalkyloxy group, each having 1 to 18 (preferably 1 to 6) carbon atoms; R 7 , R 8 , Rl0, n and m are as described above; and P is a multivalent organic group.
  • P has valence x wherein x is an integer greater than or equal to 1 (preferably between 2 and 5).
  • P has a
  • the alkoxysilane functional polyurethane of the present invention is prepared by reaction of an isocyanate functional material having the structure:
  • the alkoxysilane functional polyurethane may be tailored to provide a certain viscosity, elongation at break and other physical characteristics that are beneficial for certain applications.
  • the viscosity of the alkoxysilane functional polyurethane may be increased by increasing the molecular weight of P or by incorporating certain groups (such as dihydrourea groups) into P.
  • the viscosity may be decreased by decreasing the molecular weight of P or by incorporating other groups (such as polyoxyalkylene groups) into P.
  • higher viscosity polyurethanes may be useful to provide moisture curable putties, while lower viscosity polyurethanes may be useful to provide spray adhesives.
  • the elongation at break of a polyurethane may also be affected by the molecular weight of P as well as the value of x.
  • the elongation at break may increase as the value of x approaches 2 and/or as the molecular weight of P increases. Cured materials having high elongation of break values may be useful to provide sealants which may then be subjected to contraction and expansion.
  • the nature of the segments comprising P also affects the physical properties of the polyurethane.
  • moisture-curable hot melts are typically provided by employing a P group that comprises a polymer containing high levels of crystalline segments (such as polyhexamethylene adipate).
  • Room temperature applied adhesives are typically provided by employing a P group comprising amorphous segments (such as polypropylene glycol).
  • a moisture-curable material is needed (such as structural, contact, spray and hot melt adhesives, sealants, coatings and putties).
  • the alkoxysilane functional polyurethane of the present invention has good thermal stability and cure characteristics.
  • Figure 1 shows the 29 Si-NMR spectrum of a hydroxycarbamoylsilane of the invention (corresponding to Example 1 ) which is free from the products of an alcohol interchange reaction.
  • the large peak at ⁇ -44.9 represents the hydroxycarbamoylsilane, while the smaller peak at ⁇ -44.45 represents residual aminoalkylenealkoxysilane used to prepare the hydroxycarbamoylsilane.
  • Figure 2 shows the 29 Si-NMR spectrum of the hydroxycarbamoylsilane of Comparative Example 1 which comprised the products of an alcohol interchange reaction.
  • the large peak at ⁇ -41.4 represents the hydroxycarbamoylsilane, while the smaller peaks at ⁇ -42.5, ⁇ -43.5, and ⁇ -44.6 represent the products of alcohol interchange.
  • the hydroxycarbamoylsilane of the present invention is obtained by reaction of a substituted cyclic alkylene carbonate with an aminoalkylenealkoxysilane.
  • Useful cyclic alkylene carbonates include 4,5- dimethyl-1 ,3-dioxolan-2-one, 4,4-dimethyl-1 ,3-dioxolan-2-one, 4-ethyl-1 ,3- dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, and 4-phenoxymethyl-1,3- dioxolan-2-one.
  • the preferred cyclic alkylene carbonate is 4-methyl-1,3- dioxolan-2-one (hereinafter referred to as propylene carbonate or PC).
  • Useful aminoalkylenealkoxysilanes include 4- aminobutyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltris(2- ethylhexoxy)silane, 3-aminopropyltris(methoxyethoxyethoxy)silane, 3- aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- aminopropyldiisopropylethoxysilane, 3-aminopropyltriethoxysilane, 3-N- methylaminopropyltriethoxysilane, 3-aminopropylphenyldiethoxysilane,
  • Preferred silanes are 3-aminopropylmethyldiethoxysilane and 3- aminopropyltriethoxysilane.
  • the hydroxycarbamoylsilane is an adduct of propylene carbonate with 3-aminopropylmethyldiethoxysilane or 3-aminopropyl triethoxysilane.
  • These preferred hydroxycarbamoylsi lanes include:
  • N-(3-methyldiethoxysilylpropyl)-2-hydroxy-1 -propyl carbamate wherein R ⁇ is methyl; R 2 , R 3 , and R 4 are each hydrogen; m is 0; R 7 is hydrogen; R 8 is 1,3-propylene; R 9 is methyl; R 10 is ethyl and n is 2 in Structure I;
  • R 3 is methyl; R ⁇ , R 2 and R 4 are each hydrogen; m is 0; R 7 is hydrogen, R 8 is 1,3-propylene; R ⁇ O is ethyl and n is 3 in Structure I.
  • the reaction to produce the hydroxycarbamoylsilane is usually conducted at a temperature ranging from 15-50°C.
  • the reaction is conducted at room temperature (20-25°C).
  • Reaction temperatures below room temperature may have a tendency to diminish reaction rates, while reaction temperatures above room temperature may have a tendency to promote degradation of the products via alcohol interchange.
  • the reaction may be conducted in the absence of solvents; however, if desired, solvents such as acetone, butanone, ethyl acetate, toluene, naphtha, N-methylpyrrolidinone, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and ethylene glycol dimethyl ether may be employed.
  • solvents such as acetone, butanone, ethyl acetate, toluene, naphtha, N-methylpyrrolidinone, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and ethylene glycol dimethyl ether may be employed.
  • the reaction may be conducted without a catalyst to facilitate the attack of the carbonyl group of cyclic alkylene carbonate.
  • a catalyst such as a tin compound may be employed.
  • Reaction time will depend upon several factors, including the nature of the aminoalkylenealkoxysilane, the substituents on the cyclic alkylene carbonate, the concentration of reactants, and the temperature of the reaction. For example, the reaction of a 1 :1 molar ratio of 1 ,2-propylene carbonate and 3-aminopropyltriethoxysilane was about 90% complete after
  • the hydroxycarbamoylsilane is preferably stored in moisture-free packaging.
  • the presence of moisture can cause hydrolysis of the material, resulting in the formation of non- silane functional alcohol.
  • the hydrolysis reaction may be illustrated generically as follows:
  • the non-silane functional alcohol (ROH) interferes with the formation of a polyurethane bearing a sufficient number of moisture-reactive alkoxysilane groups.
  • the presence of competing side reactions may be determined using hydrogen nuclear magnetic resonance spectroscopy ( 1 H-NMR) and silicon magnetic resonance spectroscopy ( 2 Si-NMR).
  • the amount of non-silane functional alcohol (if any) present in the hydroxycarbamoylsilane may be determined by H-NMR).
  • H-NMR hydrogen nuclear magnetic resonance spectroscopy
  • the amount of ethanol may be calculated from the integrals of the 1 H-NMR triplet peaks corresponding to the ethoxysilane methylene ( ⁇ 3.85) and the ethanol methylene ( ⁇ 3.70).
  • a hydroxycarbamoylsilane compound that has not undergone an alcohol interchange reaction will generally exhibit one large peak in the 29 Si-NMR spectrum.
  • a compound that has undergone such a reaction will exhibit peaks corresponding to the products of the alcohol interchange reaction.
  • N-(3-thmethoxysilylpropyl)-2- hydroxyethyl carbamate exhibits one peak at ⁇ -41.5 when it has not undergone alcohol interchange, while the products of alcohol interchange exhibit additional peaks at about ⁇ -42.4, ⁇ -43.5 and ⁇ -44.6.
  • the alkoxysilane functional polyurethane of the present invention is prepared by reacting an isocyanate functional material with the hydroxycarbamoylsilane described above or hydroxycarbamoylsilanes prepared from unsubstituted cyclic alkylene carbonate.
  • the isocyanate functional material has a number average molecular weight in the range of 90 to 8,000, more preferably 2,000 to 6,000.
  • Useful isocyanate functional materials include aliphatic, cycloaliphatic, araliphatic, or aromatic isocyanates.
  • Aliphatic isocyanates usually provide adducts having good light stability while aromatic isocyanates are generally more economical.
  • Diisocyanates are preferred.
  • diisocyanates examples include 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, diphenylmethane 4,4'-diisocyanate (hereinafter referred to as MDI), 1 ,4-phenylene diisocyanate, dicyclohexylmethane diisocyanate (hereinafter referred to as H12-MDI), isophorone diisocyanate (hereinafter referred to as IPDI), 1 ,6-hexanediisocyanate, and 1 ,3-( ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl)xylylene diisocyanate (hereinafter referred to as TMXDI).
  • MDI 2,4-tolylene diisocyanate
  • H12-MDI diphenylmethane 4,4'-diisocyanate
  • IPDI isophorone diisocyanate
  • TMXDI 1 ,3-( ⁇ , ⁇ ,
  • Dimers and trimers of the above mentioned isocyanate functional compounds are also useful.
  • Preferred diisocyanate functional compounds include IPDI, MDI, and blends of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (hereinafter referred to as TDI).
  • isocyanate functional materials useful in the present invention include those wherein P of Structure 5 is itself a polyurethane.
  • a summary of basic polyurethane chemistry can be found in Polyurethane:
  • polyurethanes are produced by the condensation reaction of a polyisocyanate and an isocyanate reactive material, i.e., a branched or straight chain polymer or copolymer bearing one or more pendent or terminal isocyanate reactive groups, including hydroxyl, mercaptan, primary or secondary amine, carboxyiic acid, epoxy, acetoacetate groups, and the like.
  • the isocyanate reactive material may further bear pendant grafted miscible or immiscible polymer chains or be internally substituted with silicone segments.
  • the isocyanate reactive material may also have a molecular weight less than
  • Blends of two or more isocyanate reactive materials may also be employed.
  • Preferred isocyanate reactive materials include those having poiyalkylene ester, polyalkylene ether, polyalkylene sulfide, polyalkylene amide, polyalkylene, and polyacrylate backbones.
  • Preferred isocyanate reactive materials also include those with a backbone comprising polypropylene oxide containing very low levels of unsaturation (for example, O.07 meq vinyl/g polyol). Preparative methods for these materials are known and most are available commercially.
  • useful isocyanate reactive materials include poly(hexamethylene adipate) diol; poly(pro ⁇ ylene oxide) diol, diamine, triol, and triamine; polybutadiene diol; poly(butyl acrylate) diol; poly(ethylene oxide)-o/oc -poly(dimethylsiloxane)-b/oc c-poly(ethylene oxide) diol; poly(styrene-co-acrylonitrile)-gra ?-poly(propylene oxide) diol and triol; 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane; 1 ,4-butanediol; trimethylolpropane and water.
  • Preferred isocyanate reactive materials are polypropylene oxide) diol and triol and poly(hexamethylene adipate) diol having molecular weights in the range of from 400 to 9000.
  • alkoxysilane functional polyurethane examples include organic compounds comprising an average of at least two isocyanate groups per compound without prior chain extension and addition polymers bearing isocyanate groups.
  • useful addition polymers include copolymers comprising isocyanatoethyl methacrylate, methacryloylisocyanate, and/or 2-(3-isopropenylphenyl)-2-propylisocyanate.
  • the alkoxysilane functional polyurethane of the present invention may be prepared by condensing an isocyanate functional material with a hydroxycarbamoylsilane using procedures known in the art.
  • the molar ratio of NCO equivalents to hydroxycarbamoylsilane is 1:1.
  • a stepwise procedure is followed whereby the isocyanate functional material and hydroxycarbamoylsilane are each separately formed and then combined to form the alkoxysilane functional polyurethane.
  • the condensation reaction to form a polyurethane is typically conducted in the presence of up to 5 % by weight catalyst based on the isocyanate reactive material weight, preferably 0.00005 to 5 wt% catalyst, and more preferably 0.05 to 0.5 wt%.
  • catalysts include those listed in Polyurethanes: Chemistry and Technology. Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963.
  • Preferred catalysts are the tin IV compounds, for example dibutyltin dilaurate.
  • the stepwise reactions may optionally be carried out in the presence of solvents.
  • solvents are those which are unreactive with isocyanates and include, for example, ketones, ethers, esters, amides, hydrocarbons, chlorohydrocarbons, and chlorocarbons.
  • Specific examples of preferred solvents include acetone, butanone, ethyl acetate, toluene, naphtha, N-methylpyrrolidinone, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and ethylene glycol dimethyl ether.
  • Suitable reaction temperatures are usually between 0°C and 120°C, preferably between 25°C and 90°C, more preferably between 50°C and
  • reaction time required to convert the reactants to the desired alkoxysilane functional polyurethanes will vary widely. Reaction times will depend upon several factors, including the nature of the reactants, the concentration of reactants, and the temperature of the reaction. Progress of the reactions is readily monitored by infrared (IR) spectroscopy by following the disappearance of the isocyanate stretching frequency near 2270 cm" 1 and the growth of the carbamate carbonyl stretching frequencies near 1700 cm -1 .
  • IR infrared
  • additives may be used with the alkoxysilane functional polyurethane of the present invention to prepare composite formulations.
  • the additives may be introduced before or during the formation of the alkoxysilane functional polyurethane, provided that the additives are not isocyanate reactive. Alternately, the additives may be introduced after the alkoxysilane functional polyurethane is formed.
  • the additives are usually introduced to perform specific functions.
  • the additives may include, for example, moisture cure catalysts, plasticizers, thixotropes or antisagging agents, antioxidants, biocides, adhesion promoting agents, corrosion inhibitors, fillers (including pigments), colorants, photostabilizers, and perfumes.
  • Useful moisture cure catalysts include metal salts and complexes, amines, and organic and inorganic acids. Specific examples of useful moisture cure catalysts include dibutyltin diacetylacetonate, tetraisopropyl titanate, calcium oxide, N,N,N',N'-tetramethylguanidine, tetrabutylammonium hydroxide, trifluoroacetic acid, and dibutyl phosphate.
  • Useful plasticizers include, for example, benzoates, adipates, phthalates, sebacates, and phosphates. The plasticizers may be present at any level, although it is generally preferred that the amount of plasticizer not exceed 50% by weight. Specific examples of useful plasticizers include butyl benzyl phthalate and dipropylene glycol dibenzoate.
  • Useful thixotropes or antisagging agents include castor waxes, fumed silicas, treated clays, and polyamides.
  • the thixotrope is non-reactive with the alkoxysilane groups of the polyurethane to avoid shelf-life problems.
  • Filler may be added to alter the. color, rheology, and ultimate mechanical properties of the alkoxysilane functional polyurethane.
  • useful fillers include carbon black, calcium carbonate, titanium dioxide, iron oxide, talc, ceramic microspheres and clay.
  • the fillers are preferably free of groups which react with the isocyanate moieties of the isocyanate functional materials or the alkoxysilane moieties of the alkoxysilane functional polyurethane. Stearated, precipitated calcium carbonates are preferred fillers in applications where low cost and opacity are desirable.
  • Useful adhesion promoters include various silanes such as those available under the tradenames "A1120”, “A187", and “A189” from OS I.
  • Useful antioxidants or U.V. stabilizers include those commercially available under the tradenames "TINUVIN 770", “TINUVIN 327”, “TINUVIN 1130”, and 'TINUVIN 292", commercially available from Ciba-Geigy.
  • the alkoxysilane functional polyurethane of the present invention may be used in moisture curing, one or two part coatings, adhesives, sealants, and elastomers.
  • the alkoxysilane functional polyurethane is especially useful for providing automotive seam sealers.
  • Automotive seam sealers are typically used in high temperature environments, and as a result, must exhibit thermal stability.
  • they are typically required to adhere to surfaces such as cold rolled steel, primed steel, and galvanized steel.
  • they are typically required to accept paint shortly after application while still wet, drying to a cured film which shows no defects.
  • Automotive seam sealers typically comprise additives such as those listed above.
  • a combination of two antioxidants comprising a hindered phenolic antioxidant (such as BHT commercially available from Aldrich) and a hindered amine light stabilizer (such as Tinuvin 770 commercially available from Ciba-Geigy) is preferably used.
  • the weight ratio of hindered amine light stabilizer to hindered phenolic antioxidant is preferably about 1 :4.
  • the automobile seam sealer comprises
  • Viscosities were determined at 22°C using a Brookfield DV-1+ viscometer and are reported in Pascal seconds (Pa sec).
  • IR spectra were obtained using a Nicolet 510 FT-IR spectrometer.
  • NMR spectra were obtained using a Varion Unity 500 NMR Spectrometer.
  • the NMR Spectrometer was operated at 500 megahertz to obtain 1 H-NMR spectra and at 99.325 megahertz with an internal chromium acetylacetonate dopant to obtain the 29 Si-NMR Spectra. All NMR runs were carried out using CDCI3 solvent at 22°C using standard acquisition parameters. General information regarding the acquisition and interpretation of 29 Si-NMR spectra may be found in NMR and the Periodic Table. Chapter 10, Harris and Mann,
  • Examples 1-9 and Comparative Example 1 illustrate the preparation of hydroxycarbamoylsilanes.
  • Examples 10-29 and Comparatives 2-6 illustrate the preparation of alkoxysilane functional polyurethanes.
  • Examples 30-55 and Comparative Examples 7-10 illustrate the preparation of composite formulations comprising alkoxysilane functional polyurethanes.
  • PA PPG 4025 Arcol PPG 4025 a 4000 molecular weight polypropylene oxide diol that is commercially available from Arco, Inc. located in Newton Square
  • PA LHT-28 Arcol LHT-28 a 6000 molecular weight polypropylene oxide triol available from Arco, Inc. located in Newton Square
  • LHT-28HF Arcol LHT-28HF a 6000 molecular weight polypropylene oxide triol having a reported unsaturation level of 0.012 meg vinyl/g polyol available from Arco, Inc. located in Newton Square, PA
  • Benzoflex 9-88 a dipropylene glycol dibenzoate available from
  • Elftex ⁇ carbon black filler available from Cabot, Inc., located in Boston, MA
  • DIDP a di-isodecyl phthalate plasticizer available from
  • Tinuvin 770 a light stabilizer available from Ciba-Geigy Vulcan carbon carbon black available from Cabot black
  • A1120 N-beta (aminoethyl) gamma- aminopropyltrimethoxysilane adhesion promoter available from OSi Specialties located in Danbury, CT
  • Neostann U220 dibutyltin diacetyiacetonate curing catalyst available from Kaneka America, located in New York City, NY
  • Blend B A blend of hydroxycarbamoylsilanes comprising N-(3- methyldiethoxysilylpropyl)-2-hydroxy-1-propyl carbamate and N-(3- methyldiethoxysilylpropyl)-1-hydroxy-2-propyl carbamate was prepared. The same procedure of Example 1 was followed except that the mixture comprised 5.11 grams (0.05 moles) PC and 9.57 grams (0.05 moles) DS1505. The degree of reaction after 18 hours was 92% determined as in Example 1. The 29 Si-NMR indicated that the sample was free of alcohol interchange products. Blend B
  • a hydroxycarbamoylsilane was prepared as in Example 1 , except that an unsubstituted cyclic alkylene carbonate was used as a starting reactant and three different reaction temperatures (22°C, 50°C, and 70°C) were used. In each case, a mixture of 4.15 grams (0.05 moles) 1 ,3- dioxolan-2-one (ethylene carbonate available from Huntsman) and 11.07 (0.05 moles) A1100 was allowed to react. The conversion of carbonate to carbamate and degree of alcohol interchange were determined as in Example 1 and are reported in Table 2.5. The mole percent of ethanol present in the hydroxycarbamoylsilane was determined using 1 H-NMR and is reported in Table 2.5.
  • Examples 9B-9C comprised EtOH. Since the 29 Si-NMR indicated the absence of alcohol interchange, the EtOH is believed to be present due to hydrolysis of the material.
  • a hydroxycarbamoylsilane was prepared as in Example 1 , except that a 3-aminopropylthmethoxysilane (A1110) was used as a starting reactant.
  • a mixture of 5.11 grams (0.05 moles) PC and 8.96 grams (0.50 moles) A1110 was allowed to react at 22°C for about 20 hours.
  • An isocyanate functional polymer was formed by preparing a homogeneous mixture of the following ingredients:
  • EXAMPLES 11-15 Preparation of Alkoxysilane Functional Polyurethanes Using Various Isocyanate Functional Starting Materials
  • the same procedure of Example 10, Part I was repeated five times, except that each time a different organic isocyanate compound was used to prepare the isocyanate functional polymer.
  • the five different organic isocyanate compounds are identified in Table 3.
  • the quantity of organic isocyanate compound (0.266 equiv. NCO) given in Table 3 was allowed to react with 280 grams of PPG 4025 (0.142 eq OH) and 70 grams of LHT-28 (0.036 eq OH) in the presence of 0.35 grams DBTDL catalyst.
  • the viscosities of the resulting isocyanate functional polymers were measured and can be found in Table 3.
  • Ratio A1100 PC Weight (mol) Blend Ratio
  • alkoxysilane functional polyurethanes were prepared using the procedure of Example 10, Part III, by reacting each of the blends described in Table 4 with 34.50 grams (0.008 eq NCO) isocyanate functional polymer prepared as in Example 15. The amount of HyCS: A1100 blend used in the reaction and the viscosities of the resulting alkoxysilane functional polyurethanes are listed in Table 5.
  • An isocyanate functional polymer having a low unsaturation level was formed by preparing a homogeneous mixture of the following ingredients:
  • Blend A (0.009 mol) prepared in Example 2 was reacted with 38.82 grams (0.009 eq NCO) of an isocyanate functional polymer prepared as in Example 15, using the same procedure given in Example 10, Part III, to form an alkoxysilane functional polyurethane.
  • EXAMPLE 22 Preparation of Alkoxysilane Functional Polyurethane
  • An isocyanate functional polymer was formed by preparing a homogeneous mixture of the following ingredients: 30.72 grams (0.004 eq OH) PPG 4025, 7.68 grams (0.004 eq OH) LHT-28,
  • HyCS HyCS 10
  • N-methylpyrrolidinone available from Mallinckrodt located in Paris, KY
  • the N-methylpyrrolidinone was added to reduce the viscosity of the mixture.
  • the mixture was agitated and held at 70°C for 18 hours and found to have a Brookfield viscosity of 160 Pa sec.
  • alkoxysilane functional polyurethanes may be derived from polyols having different molecular weights.
  • EXAMPLES 27-29 Preparation of Alkoxysilane Functional
  • a set of isocyanate functional polymers having different molecular weights was prepared by combining the quantity of IPDI listed in Table 7 with 40 grams (0.019 eq OH) of PPG 4025 to form a homogeneous mixture. To this homogeneous mixture, 0.08 grams of DBTDL was added. The atmosphere was inerted with nitrogen, and the mixture was agitated and heated to 70°C to form an isocyanate functional polymer. The resulting isocyanate functional polymers were subsequently converted to a corresponding set of alkoxysilane functional polyurethanes, following the procedure of Example 10, Part III. The quantities of HyCS used and the viscosity of the resulting alkoxysilane functional polyurethanes are given in Table 7. Table 7
  • alkoxysilane functional polyurethanes may be derived from isocyanate polymers having different molecular weights to achieve different end-product viscosities.
  • COMPARATIVE EXAMPLES 2-6 Alkoxysilane Functional Polyurethane Prepared from an Amine Functional Alkoxysilane.
  • Each of the isocyanates (0.009 eq NCO) of Examples 11-15 (TDI, MDI, H12- DI, TMXDI, and IPDI) was allowed to react with 1.99 grams (0.009 mol) A1100 (in place of HyCS) using the same procedure of Example 10, Part III.
  • the quantity of each of the isocyanate functional polymers used in these reactions was the same as that used in the reactions of Examples 11-15 and may be located in the fifth column of Table 3.
  • Table 8 provides the viscosities of the alkoxysilane functional polyurethanes based on the amine functional alkoxysilane. A comparison of the viscosities of Table 3 with those of Table 8 indicates that lower viscosities are achieved with the present invention. This is important in providing materials that may be used in a variety of applications where lower viscosity is preferred.
  • Creamy dispersions of the following ingredients were made using a 42 mm diameter, saw tooth, dispersing blade (available from Premier Mill located in Reading, PARAGRAPH):
  • Example 30 The general procedure of Examples 30-48 was repeated, except that an antioxidant was incorporated into the moisture curable material.
  • a dispersion was prepared by adding 144 grams Ultrapflex to a homogenous blend of 25.6 grams Benzoflex 9-88 and 144 grams of an alkoxysilane functional polyurethane prepared as in Example 15. A solution containing 0.11 grams BHT and 0.50 grams Benzoflex 9-88 was added to 25.4 grams of the dispersion.
  • Neostann U220 (0.11 grams) was added, and the moisture curable material was poured into an aluminum dish to a depth of 8 mm. The sample was allowed to cure at 25°C and 50% relative humidity for 18 hours and then was held at 85°C and 15% relative humidity for 16 days. The material remained elastomeric and retained a smooth, glossy, tack-free surface, thus demonstrating good thermal stability and cure characteristics.
  • COMPARATIVE EXAMPLES 7-9 COMPARATIVE EXAMPLES 7-9
  • Example 30 The same composite of Example 30 was prepared, except for the use of a HyCS of Example 1 which was forced to undergo alcohol interchange by heating to 110°C for 22 hours. 29 Si-NMR and 1 H-NMR indicated that the HyCS was contaminated with 16 mole percent EtOH, 10 mole percent from an alcohol interchange reaction.
  • the composite had a viscosity of 565 Pa sec.
  • a tacky product resulted from attempts to cure the composite by exposure to ambient conditions for one week at 20-25°C.
  • the resulting material had a tensile strength of 1900 kPa, an elongation of 480% and a tear strength of 1 kN/m. A comparison of this data with that of
  • Example 30 (in which HyCS of Example 1 showing no alcohol interchange was used) demonstrates the advantages of the present invention. More specifically, the composite of Example 30 had a viscosity of 530 Pa sec, a tensile strength of 5400 kPa, an elongation of 490% and a tear strength of 16 kN/m. Thus, the composite prepared from the HyCS had a higher tensile and tear strength than one prepared from HyCS that was contaminated with 16 mole percent EtOH.
  • EXAMPLE 55 Preparation of an Automotive Seam Sealer
  • a composite material for sealing automobile body seams was prepared in this example. Seam sealers are frequently used in the automotive industry to cover the interface formed by two overlapping pieces of metal. The seam sealer provides corrosion resistance to and improves the aesthetic appearance of the overlap area.
  • a 4 gallon high shear Myers mixer was flushed with nitrogen and filled with the following components:
  • Dislon 6500 thickener 100 grams Dislon 6500 thickener. The components were mixed at high speed for 5 minutes while under a nitrogen blanket. To this, 500 grams of Ultrapflex (previously dried overnight at 104°C (220°F)) were added and mixed at high speed under nitrogen for 20 minutes while heating the mixture to 77-82°C (170-180°F). To this, 5300 grams of Zeeospheres 600 (previously dried overnight at
  • the seam sealer was tested for tack free time, hardness, adhesion, wet-on-wet paintability and shelf-life using the following test procedures: Tack Free Time
  • a 0.64 cm (0.25 in) diameter, 22.9 cm (9 in) long bead of seam sealer was applied to a cold rolled steel panel (30.5 cm (12 in) x 10.16 (4 in)) that had been cleaned by wiping first with methyl ethyl ketone, then with toluene, and then again with methyl ethyl ketone.
  • the bead was allowed to cure for one week in a controlled environment having a temperature of 21 °C (70°F) and a relative humidity of 50%.
  • One end of the bead was cut away from the steel panel to form a free end. The free end was pulled, and the failure mode of the sealer was noted. Cohesive failure occurred when the sealer split apart, leaving sealer residue on the panel. Adhesive failure occurred when the sealer lifted off the panel, leaving no residue. Of these two modes of failure, cohesive failure is preferred. Cold Flexibility
  • a panel bearing a bead of cured sealer was prepared as described above for the adhesion test.
  • the panel was placed in a -20°C (-4°F) refrigerator for one hour.
  • the panel was then bent 180 degrees over a 2.54 cm (1 in) diameter rod.
  • the sealer failed this test if it pulled away from the panel without leaving any residue (i.e., adhesive failure) or if it showed any cracks at the point of bending.
  • a 0.64 cm (0.25 in) diameter, 22.9 cm (9 in) long bead of seam sealer was applied to a cold rolled steel panel (30.5 cm (12 in) x 10.16 (4 in)) that had been cleaned by wiping first with methyl ethyl ketone, then with toluene, and then again with methyl ethyl ketone. The bead was then smoothed to form a 0.16 cm (0.063 in) thick film. Paint (PPG Deltron base clear available from Pittsburgh Paint & Glass, Inc. located in Strongsville, OH) was then applied to the film immediately after application in one case and after 60 minutes in another case. The painting sequence was per the manufacturer instructions: One part base coat was mixed with 1.5 parts reducer.
  • a cartridge of sealer was tested for tack free time, hardness, adhesion, cold flexibility, and viscosity and then stored in a 120°F oven for four weeks. The sealer was then re-tested. If no significant change in the test results were observed and if the sealer showed no product separation after aging, then the sealer was considered to have good shelf life.
  • Cartridges used for aging comprise either aluminum or high density polyethylene.
  • the seam sealer of this example gave a tack free time of 22 minutes, an initial hardness of 29, a final hardness of 46, and cohesive failure in the adhesion test.
  • the seam sealer also passed the cold flexibility test and provided wet-on-wet paintability and good shelf life.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Sealing Material Composition (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/US1996/005433 1995-06-02 1996-04-19 Hydroxy functional alkoxysilane and alkoxysilane functional polyurethane made therefrom WO1996038453A1 (en)

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JP53646196A JP4016090B2 (ja) 1995-06-02 1996-04-19 ヒドロキシ官能性アルコキシシランおよび該アルコキシシランから製造されたアルコキシシラン官能性ポリウレタン
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KR19990022079A (ko) 1999-03-25
US5587502A (en) 1996-12-24
CA2220337A1 (en) 1996-12-05
DE69601634T2 (de) 1999-07-29
DE69601634D1 (de) 1999-04-08
EP0833830A1 (en) 1998-04-08
JP4016090B2 (ja) 2007-12-05
EP0833830B1 (en) 1999-03-03
JPH11511748A (ja) 1999-10-12

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